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United States Patent: ?tice
3,066,151
Patented Nov. 27, 1962
1
2
3,066,151
cyclopentadiene esters from which the‘ product epoxy
POLYCYCLOPENTADIENES
esters are prepared. The acids preferred include satu
rated and unsaturated monocarboxylic acids having 1
L and James A. Gallagher, Cranford, N.J., assignors to
sso ofResearch
and. Engineering Company, a corpora
tion
Delaware
preferred. Examples of suitable saturated acids‘ are
EPOXY ESTERS DERIVED FROM
John P. Thorn, Union, William A. Dimler, Jr., Colonia,
to 26, or more, carbon atoms.
formic, butyric, Valerie, caproic, caprylic, capric, lauric,
N0 Drawing. Filed Sept. 29, 1958, Ser. No. 763,815
palmitic, stearic,
3 Claims. (Cl. 260-348) _
'
Examples of suitable
unsaturated acids are crotonic, undecylcnic, oleic, erucic,
10
This invention relates to epoxidized polycyclopenta
diene derivatives. More particularly, the invention re
lates to epoxidized polycyclopentadiene esters, which es
The polycyclopentadienes may be reacted directly with
ters have been found to be especially useful plasticizers
and stabilizers for synthetic resins._
The C6—C20 acids are
the above acids to form the
‘
Speci?cally, the invention provides a new class of poly 15
cyclopentadiene esters having an oxirane ring substituted
as taught by Bruson in US. Patent 2,385,788, which al
for the residual ethylenic group in the polycyclopenta
cohol is then reacted with the acids to form the esters.
The latter method is preferred because it normally leads
is a dicyclopentadiene ester epoxide having the formula:
to higher yields of the esters.
20
The unsaturated esters of this type may be represented
diene ring structure. An example of the new epoxy esters
by the following formula:
25
wherein R contains up to 25 carbon atoms, preferably 5
30
to 19 carbon atoms, and represents the carboxylic
wherein n is an integer ‘between 0 and 2, RCOO+ is the
residue of an aliphatic carboxylic acid containing 1 to
35 26 or more carbon atoms.
The acids of which R—CO‘ “—
C1-C4 alkyl groups. The preferred esters. are the di
cyclopentadiene esters, i.e., Where n is 0.
»
For the direct e’steri?cation,
45
‘crack to Above about 150° C., the dicyclopentadienes
the monomers. Preferably the reaction tem
perature 'is from 50° to 125° C.
Unless the monobasic
50,
55
The polycyclopentadienes from which the present esters
tri-, tetra-cyclopentadienes
Dicyclopentadiene and the
C1-C4 alkyl' substituted dicyclop'entadlenes are preferred.
cylopentadiene, and dimethyl dicyclopentadiene.
60
means such‘ as
When the polycyclopentadienes are hydrolyzed prior to
esteri?cation, the polycyclopentadiene is reacted with at
least about an equimolecular amount of water in the pres
The above polycyclopentadienes are reacted with ali 65 ence
of a mineral acid catalyst. Preferably about 2 to 20
moles of water, as .part of a dilute sulfuric acid solution,
e'.g. 20-50% H2804, are reacted per mole of polycyclo
phatic carboxylic acids .to form ‘the,
'
A
'
_
4
3,066,151
3
cizers, with the latter generally comprising at least about
pentadiene. Again only the double bond of the endo
methylene ring of the polycyclopentadienes is hydrolyzed,
the remaining double bond remaining inactive. The by
drolysis temperature may vary from about 60° to 120°
25% of the total plasticizer. As a stabilizer, about 0.1 to
10 parts by weight of the present esters are employed per
100 parts of resin. Other stabilizers, lubricants, pig
ments, clari?ers, HCl acceptors, and the like may be
C., depending on the concentration of H2504. Preferably
a re?ux temperature of about 100°-110° C. is main
employed if desired.
The invention is further illustrated by the following
tained. The resulting polycyclopentenyl alcohol may be
examples, which are not intended to limit the scope of
recovered by conventional means, e.g. distillation, extrac
the invention.
EXAMPLE 1.——PREPARATION OF DICYCLO
PENTADIENE OLEATE EPOXIDE
tion, etc.
alcohol is then esteri?ed with the mono 10
carbox he acid in the conventional manner. At least an
equimolecular amount of the alcohol is heated with the
A. Oleic acid (282.5 g., 1.0 mole) was esteri?ed with
acid to a temperature varying from about 80° to 220° C.
an excess (180 g., 1.2 moles) of hydroxydihydronordi
Preferably a molar ratio of alcohol to acid of 1:1 to 2:1, 15 cyclopentadiene. (This alcohol is readily prepared from
120° to 150° C.
dicyclopentadiene.) Toluene (75 ml.) was the entrainer
and an esteri?cation temperature from
and toluene sulfonic acid (16 g., 4 wt. percent based on
are employed.
Catalysts are not necessary for this esteri?cation reac
theoretical ester) was the catalyst. The reaction was
tion, but may be used, if desired, to speed up the reaction.
run at l08°-115° C. for 1.5 hours until the theoretical
Suitable catalysts are sulfuric acid, p-toluene sulfonic 20 amount of water (18 ml.) was azeotroped off. A minor
acid, benzene sulfonic acid, phosphoric acid, etc. En
portion (about 5 g.) of calcium hydroxide was added
trainers or azeotrope agents such as benzene, toluene,
hexane, heptane, etc. may also be used, or the excess alco
to precipitate any unreacted oleic acid as its calcium salt,
which was ?ltered oil. The reaction mixture was then
hol in the reaction mixture may be used for entraining the
washed with 5% caustic, then with salt water until
water. The esters may be recovered by usual means, such 25 neutral, and the excess alcohol was removed by distilla
as distillation, solvent extraction, etc.
tion.
The resulting cyclic esters all have a residual double
B. Sodium acetate (4.8 g., 0.06 mole) and the ester
bond located in the terminal cyclopentadiene ring. Nor
(124.2 g., 0.30 mole) were maintained at 25° C. for 35
mally this double bond is essentially inert, as evidenced
minutes as an excess of peracetic acid (116.4 g. of a 40%
by its inability to be hydrolyzed. The essence of this in 30 solution) was added. The mixture was stirred two hours
at 25° C. and one hour at 50° C. After washing until
vention lies in the epoxidation of that residual double
bond in order to form a compatible and more stable com
neutral and drying over Na2SO4, a 97% yield of the epox
pound. Other double bonds located in the acid groups,
idized ester was obtained. Titration for oxirane oxygen
occurring when an unsaturated acid is employed in pre
by HBr in glacial acetic acid showed about 1.5 oxirane
35 groups per molecule. However, it is believed that this
paring the ester, may also be epoxidized.
The epoxidation may be accomplished by reacting the
reagent is not capable of detecting all of the oxirane rings
unsaturated ester with a peroxidizing agent. The tem
on the dicyclopentadiene ring. Thus it is believed that
perature of reaction may vary over the range of —-30° C.
both the double bond in the ring and the double bond in
the residual acid group were substantially completely
to +100° C., but preferably the temperature is kept be
low room temperature, e.g. between about ——10° C. and 40 epoxidized.
20° C.
EXAMPLE 2.——DICYCLOPENTADIENE OLEATE
Suitable peroxidizing agents are hydrogen peroxide and
the organic peracids, e.g. performic acid, peracetic acid,
EPOXIDE AS A PLASTICIZER 1N POLYVINYL
perbenzoic acid, monoperphthalic acid, etc. The reac
tion is essentially quantitative. The amount of peroxidiz
CHLORIDE
Polymer compositions were formulated according to
the following recipe:
ing agent employed may vary from about 1 to 2 moles
per ethylenic group in the ester. Preferably, at least an
equimolecular amount and not more than a slight excess
Ingredient:
of the peroxidizing agent is employed.
The resulting epoxy esters may be recovered by any 50
convenient means such as distillation, extraction, etc. The
epoxides are relatively high boiling liquids.
The epoxy esters of this invention are particularly valu
able as plasticizers and stabilizers for synthetic resins.
The unexpected epoxidation of the normally inactive
Parts by weight
Polyvinyl chloride _____________________ .. 100
Plasticier ____________________________ __
Ba-Cd phenate ________________________ __
Stearic acid ___________________________ __
55
50
2
0.5
The stearic acid serves as a lubricant, and the Ba-Cd
double bond of the polycyclopentadiene esters has led to
phenate as an vauxiliary stabilizer (HCl acceptor). Other
an epoxy ester which is compatible with vinyl and other
auxiliary stabilizers and pigments may be added as long
resins. Furthermore, it is believed that the position of
as the only variable in the runs is the plasticizer em
the epoxy group on the ring structure of the polycyclo
ployed.
pentadiene ester is an important factor in the attainment 60 The test samples were prepared by mixing the above
of the high degree of stability in the present epoxy esters.
ingredients on an 8 x 16 in. mill for 5 minutes at 320° F.
The synthetic resins in which the present epoxy esters
Sheets were calendered and cut into 6 by 6 in. slabs for
are most useful are those which are unstable to heat and
molding. The molding procedure consisted of pressing
light. The vinyl-type resins, especially those having acid
the sheets in a mold at minimum pressure (e.g. 50-100
forming elements, are representative of such unstable 65 p.s.i.) for 10 min. at 320° F., and then at high pressure
resins. The most important of these resins are polyvinyl
chloride and copolymers of vinyl chloride with vinyl ace
tate, vinylidene chloride, ethyl maleate, etc.
(e.g. 2100 p.s.i.) for 7 minutes at 320° F. and cooling
the slab in the mold under pressure. Physical properties
and color stability were determined on specimens 0.075
The present epoxy esters may be used as plasticizers by
in. thick.
themselves, as coplasticizers with other suitable plasti 70 Four runs were made: one (Run A) in which the sole
plasticizer was the commercially available didecyl phthal
cizers, or solely as stabilizers. When used as the sole
ate (DDP); a second (Run B) in which the plasticizer
plasticizer, the esters are employed in amounts varying
consisted of 50% DDP and 50% of isooctyl oleate epox
from 25 to 75 parts by weight or more per 100 parts of
ide (C8 oleate epoxide) which is a commercial resin plas-v
resin. The same proportion of total plasticizer is gen
erally used when the present esters are used as coplasti
3,066,151
6
Other stabilizers, etc., may 'be added as long as the
only variable in the runs is the stabilizer employed. The
oleate) prepared in part A of Example 1; and a fourth
oleate epoxide) prepared in part B of Example 1
The
results are shown in Table .
Table IL-Dicyclopentqdiene ‘Oleate Epoxide as
Stabilize)‘
Table I.—Dicyclopentadiene Oleate Epoxide as
10 Run _______________________________ _-
Plasticizer
Run _______________________________ __
Plasticizer
effect of the various stabilizers on the polymer upon ex
posure to heat and ultra violet light is shown in Table II.
A
Tensile strength, p.s
oleate
epoxicle
Elongation, percent ____________ __
300
320
olumc resistivity,
Physical
prop. afterohm-cm.><l0—13___
aging (7 days at
2. 7
3. 6
20
212° F.).'
Tensile strength, p.s.l ______ __
Elongation, percent- _
Original
color 1 3_____________________
__
Heat stability‘
4
45
G
None
Ca
oleate
DCP
oleate
DCP
oleate
____ __ 2, 690
Elongation, percent.
Original physical prop.:
2, 760
F
epoxide
epoxide
15 Original physical prop;
P+ DDP+
DCP
Tensile strength, p.s.i __________ _- 2, 690
E
Stabilizer
D
DDP
A
-_
2, 730
2, 660
2, 740
___
300
310
310
315
Volume resistivity,
13"
Physical
prop. alterohm-cm.><l
aging, (7 days
2. 7
2. 9
2.8
2.4
at 212° F.):
Tensile strength, p.s.i __________ __ 2, 600
Elongation, percent__
Original color 1 _ _ _ _ _ _ _ _ _
Heat
stability? 4
265
2, 650
2, 520
2, 640
1
1. 5
Z 2
. _ _ _ _ __
gig min ___________ __
min.._
90 min-
2, 710
290
1
0+
0
295
280
0
i‘ 51/2
'
0
0
0
1.
0
0
.
0
_
_
_--.
0+
@ Incompatible.
1 Gardner color.
"'IM
Table II shows
'
from
esters may be used in minor
1 Original color due to dark color of the DCP oleate epoxide used; this
epoxide has been obtamed as a colorless product.
1 737 giéat stability determined by heating in forced-draft
air oven at 35
light stabilizers.
4 Heat stability scale based on degradation of color: 0=no color degra
dation; 1=sligl1tly yellow; 2=yellow; 3=dark yellow; 4=dark
orange;
_
_
_
5=dark brown or black.
5 Light stability determined by
Fadometer;
ASTM D~750—43—’I‘.
exposure to ultra vlolet light In a
?Light stability scale based on degradation of color and appearance:
0=no degradation; 1=slightly yellow and/or slightly spotted; 2=yell0w
and/or and/or
moderately
and/or black spots; 4=dark
orange
almostspotted;
entirely3=dark
spotted;yellow
5=black.
45
'50
55
EXAMPLE 3.~DICYCLOPENTADIENE OLEATE
EPOXIDE AS A STABILIZER IN POLYVINYL
CHLORIDE
0 wherein R is an alkyl oxirane group containing up to
25 carbon atoms.
2. An epoxy ester having the formula
Ingredient:
Parts by weight
Polyvinyl chloride _____________________ __ 100
Didecl phthalate plasticizer_____________ __
Stabilizer ____________________________ __
Ba-C-d phenate ________________________ __
Stearic acid ___________________________ ___.
45
5
2
0.5
70
QEOI
bio‘
wherein R is an alkyl oxirane group containing 5 to
75 19
carbon atoms.
-
295
0
+
+
‘
3,066,151
References Cited in the ?le of this patent
3. An epoxy ester having the formula
UNITED STATES PATENTS
‘3
H2O
Niederhauser ________ __ Feb. 27, 1951
/ \H
\
C
\
0
\ °H=\
m-coo-o
H
C\
\/
0
memo/K
"H
H2
2,543,419
Dazzi ______________ __. Aug. 24, 1954
2,723,247
Harrington __________ __ Nov. 8, 1955
Frostick et a1. ______ __ Mar. 19, 1957
2,687,389
2,786,066
2,794,030
2,794,812
Phillips et a1. ________ __ May 28, 1957
Phillips et a1. ________ __ June 4, 1957
Notice of Adverse Decision in Interference
In Interference No. 94,462 involving Patent No. 3,066,151, J. P. Thorn,
WV. A. Dimler, J r., and J. A. Gallagher, EPOXY ES'TERS DERIVED
FROM POLYCYCLOPENTADIENES, ?nal judgment adverse to the
patentees was rendered Sept. 14, 1965, as to ‘claims 1, 2 and 3.
[O?eial Gazette December 14, 1.965.]